Poly(ether esters) of phthalic acid salts and di(haloalkyl) ethers as dye receptive agents

ABSTRACT

Poly(ether esters) are prepared by reacting a phthalic acid salt with a di(haloalkyl)ether in a polar solvent using a phosphonium salt catalyst. The resulting poly(ether esters) are useful in olefin polymers to improve dye receptivity.

United States Patent 1 Brady et al.

POLY(ETHER ESTERS) OF PHTHALIC ACID SALTS AND DI(HALOALKYL) ETHERS ASDYE RECEPTIVE AGENTS Inventors: Donnie G. Brady; Harold R. Deck;

Faber B. Jones, all of Bart-lesville, 0kla.; John H. Underwood,Charlotte, N.C.

Assignee: Phillips Petroleum Company Filed: June 16, 1971 Appl. No.:153,866

US. Cl ..260/873, S/DIG. 9, 260/75 H, 260/93.7, 260/949 GD, 260/475 RInt. Cl. ..C08g 39/10, D06p 3/00 Field of Search ..260/75 R, 75 H, 475R, 873, 260/949 GD, 93.7; 8/DIG. 9

. 51 Feb. 13, 1973 Primary Examiner-William H. Short AssistantExaminerEdward Woodberry Att0rney-J. Arthur Young et al.

57 ABSTRACT Poly(ether esters) are prepared by reacting a phthalic acidsalt with a di(haloalkyl)ether in a polar solvent' using a phosphoniumsalt catalyst. The resulting poly(ether esters) are useful in olefinpolymers to improve dye receptivity.

6 Claims, No Drawings POLY(ETI-IER ESTERS) OF PHTIIALIC ACID SALTS ANDDI(HAL OALKYL) ETHERS AS DYE RECEPTIVE AGENTS BACKGROUND OF THEINVENTION great variation from polymer to polymer as to what is or isnot effective in improving dye receptivity. Olefin polymers such aspolypropylene present the greatest challenge to the dyeing art becauseof their chemical inertness and general nonpolar character.

SUMMARY OF THE INVENTION DESCRIPTION OF THE PREFERRED EMBODIMENTS Thepoly(ether esters) of this invention can be made by reacting a phthalicacid salt with a di(haloalkyl) ether in a polar solvent utilizing aphosphonium salt catalyst.

The phthalic acid salt can be either the ortho, meta, or the para. Theisophthalic or terephthalic are preferred with the terephthalate beingmost preferred. The ammonium or any Group 1 metal salt can be usedalthough the sodium, potassium, lithium, and rubidium salts arepreferred. Exemplary salts are dipotassium isophthalate, disodiumisophthalate, diammonium terephthalate, dilithium phthalate, dirubidiumterephthalate, and the like.

The di(haloalkyl) ether can be represented by the following formula:

wherein X is a halogen selected from the group consisting of chlorine,bromine, and iodine, preferably chlorine or bromine; and R and R arealkylene groups containing one to six carbon atoms with no branching atthe carbon atom to which the halogen atom is attached. Symmetric ethersare preferred wherein R and R are identical. Exemplary of suitableethers are bis(2- bromoethyl) ether, bis(3-chloro-2-methylpropyl) ether,bis(4-chlorobutyl) ether, bis(4-bromo-2- ethylbutyl) ether, andbis(6-chlorohexyl) ether. Also ethers such as 2-chloroethyl4-chlorobutyl ether can be utilized. The preferred ether isbis(chloromethyl) ether.

Any polar organic solvent which is nonreactive under the reactionconditions may be employed as the solvent. The preferred polar solventsare tertiary amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-N-phenylformamide, N- methylpyrrolidone, andnitriles such as acetonitrile and propionitrile. Alternatively, anexcess of di(haloalkyl) ether can be used as the solvent. The preferredsolvent is N,N-dimethylformamide.

The phosphonium catalyst is phosphonium salt having the formula aquaternary wherein R is a hydrocarbyl radical and can be alkyl,cycloalkyl, aryl, or combinations thereof such as am]- kyl, alkaryl, andthe like, containing from one to eight carbon atoms. The R groups withina given phosphonium salt need not all be the same. As an example, thepreferred material is ethyltriphenylphosphonium bromide. m is an integerfrom 1 to 3 and is equal to the valence of Y. Y can be selected fromother anionic group having a valence of 1 to 3 that is not deleteriousto the formation of the poly(ether ester). R is like R in all respectsexcept that'R has a valence of 2 and has a range of six to 10 carbonatoms. Examples of suitable phosphonium catalysts includetetrabutylphosphonium nitrate, ethyltriphenylphosphonium bromide,p-tolyltrimethylphosphonium phosphate, and di(tetrabutyl)phosphoniumsuccinate.

The mole ratio of phthalate salt to di(haloalkyl) ether is preferablyabout 1:1 to promote development of long polymer chains of poly(etherester). The mole ratio of phosphonium salt catalyst to phthalate saltshould be in the range of 0.01 to 25 moles of phosphonium salt catalystper l00 moles of phthalate salt, preferably 0.1 to 10 moles ofphosphonium salt catalyst per moles of phthalate salt.

The reaction temperature can vary broadly from 20 to 300 C, preferablyfrom about 2 to 6 hours. The weight average molecular weight can varyfrom 1,000 to 1,000,000, preferably 2,000 to 100,000, more preferably2,000 to 10,000.

The poly(ether ester) of this invention can be represented by theformula where R and R are alkylene groups containing one to six carbonatoms as defined above with no branching on the carbon atom attached tothe oxygen of the carboxy group, and m is an integer sufficient to givethe polymer weight average molecular weight of at least 1,000.

The olefin polymers which can'be improved in dye receptivity throughincorporation of the poly(ether ester) of this invention include anyolefin polymer particularly polymers and copolymers of mono-l-olefinshave two to eight carbon atoms per molecule, more preferablypolypropylene.

The amount of poly(ether ester) dye receptive agent blended into thepolyolefin will generally be in the range of from about 1 to about 25weight percent based on the weight of the polyolefin, preferably 5 toweight percent. The additive can be incorporated into the polymer in anyconventional manner such as mill blending, solution blending and thelike. Other conventional additives can be in the olefin polymer such asantioxidants, UV stabilizers, pigments or fillers, foaming agents, andthe like.

EXAMPLE 1 Synthesis of Po1y(2-oxapropyleneterephthalate) A mixture ofdipotassium terephthalate (55.04 g, 0.227 mole) andethyltriphenylphosphonium bromide (4.0 g, 0.01 mole) inN,N-dimethylformamide (225 ml) was stirred and warmed to 70 C under anitrogen atmosphere. A solution of freshly distilled bis(chloromethyl)ether (26.1 g, 0.227 mole) in N,N dimethylformamide (100 ml) was addeddropwise to that mixture over 0.5 hour period. The temperature was thenraised to and maintained at 100 C for 4 hours, cooled to roomtemperature and poured into 400 ml of distilled water. The resultingwhite solid was collected by filtration, air-dried and then washed byslurrying it successively in distilled water, methanol, distilled water,and methanol. The white, powdery product was dried at 120 C in a vacuumoven to afford a 43.6 g (92) yield of poly(2-oxapropyleneterephthalate),rn.p. approximately 190 C. The reaction can be depicted as follows:

+ ClC'HeO CHzCl The poly(ether ester) of Example I was tested as a dyereceptive agent in the following composition:

A phenolic antioxidant A benzotn'azole type ultraviolet stabilizer Theabove composition was pelletized, spun, drawn (2.5:1), knit into a sockand the spin finish was removed. Six inch samples of knit were dyed (2.0on

weight of fiber).

The dyeing procedure involved Jsihg'a dysohiion (2 percent dye, 2percent Dupanol RA, which is an alcohol ether sodium sulfate anionictextile detergent, 40:1 liquor ratio) at 205-2l0 F into which the sockwas repeatedly lowered, raised; and relowered for 1 hr.

Following rinse and after-scour (15 minutes repeatedly lowering, raisingand relowering into a bath of F containing 2 percent of anionicsurfactant), the sock was dried and examined. The results are tabulatedbelow.

I TABLE ll Color Light Dry Sample Dye" Yield Fastness Cleaning Unmod. PPA 3.1 2/5 0 Mod. PP A 5.1 4/40 l-2 Unmod. PP B 2.6 2/5 0 Mod. PF 8 5.14/20 2 Unmod. PP C 1.3 2/5 0 Mod. PP C 3.3 4/40 2 (I) A Genacron l3lueGR, B Polydye Red BC, C Calcosyn Yellow GCN; (all dyes employed at 2 wt.on fiber).

(2) Determined by lDL Color Eye (the higher the number, the deeper thecolor).

(3) An AATCC standard test (exposure in Weatherometer: the higher thenumerator, the more intense the remaining color; the denominator" equalsthe number of hours to appreciable failure).

(4) An AATCC standard test (0 denotes total loss of color, 5 woulddenote full retention of color).

(5) Unmodified polypropylene (no dye receptor).

(6) Modified polypropylene (composition shown in Table l).

The value of po1y(2-oxapropyleneterephthalate) as a dye receptor isclearly shown in Table 11 with all dyes in all tests by the superiorityof the modified over the unmodified samples.

While this invention has been described in detail for the purpose ofillustration, it is not to be construed as limited thereby but isintended to cover all changes and modifications within the spirit andscope thereof.

We claim:

I. A composition comprising a polymer of at least one mono-l-olefinhaving two to eight carbon atoms per molecule and from 1 to 25 weightpercent based on the weight of said olefin of a poly(ether ester)consisting essentially of recurring units as represented by thefollowing formula spa.

4 A composition according to claim 2 wherein the ether portion of saidpolymer is symmetric.

5. A composition according to claim 2 wherein said poly(ether ester) ispoly(2-oxapropyleneterephthalate). 5

6. A composition according to claim 5 wherein saidpoly(2-oxapropyleneterephthalate) is present in an amount within therange of 5 to weight percent.

1. A composition comprising a polymer of at least one mono-1-olefinhaving two to eight carbon atoms per molecule and from 1 to 25 weightpercent based on the weight of said olefin of a poly(ether ester)consisting essentially of recurring units as represented by Thefollowing formula
 2. A composition according to claim 1 wherein saidolefin polymer comprises polypropylene.
 3. A composition according toclaim 2 wherein said poly(ether ester) is present in an amount withinthe range of 5 to 15 weight percent.
 4. A composition according to claim2 wherein the ether portion of said polymer is symmetric.
 5. Acomposition according to claim 2 wherein said poly(ether ester) ispoly(2-oxapropyleneterephthalate).